Lithium Sulphite Electrode Synthesis for Supercapacitors

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Solution Overview

Problem

Conventional methods for synthesizing lithium sulphite are hazardous due to the use of corrosive sulphur dioxide and flammable hydrogen gases, and existing supercapacitor electrode materials suffer from low energy density and high resistance.

Innovation Solution

A process involving the reaction of sulphurous acid with lithium carbonate under an inert atmosphere to form lithium sulphite, which is then combined with a nitrogen-carbon structure to create a precursor electrode material for supercapacitors, allowing for the formation of SO3 complexes that enhance capacitance and energy density.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If conventional methods are used to synthesize lithium sulphite, then lithium sulphite can be produced, but the process involves hazardous corrosive sulphur dioxide and flammable hydrogen gases

Engineering Contradiction:
Improvesafety of synthesis processVSAvoidhazardous gases (sulphur dioxide and hydrogen)
Core Design Contradiction:
ReliabilityVSObject-affected harmful factors

Solution Approach 1:

The patent uses sulphurous acid as an intermediary substance to replace the direct reaction between sulphur dioxide and hydrogen with lithium carbonate. This intermediary approach eliminates the need for hazardous gases while achieving the same chemical transformation, as sulphurous acid can be handled more safely and decomposes to provide the necessary sulphite ions.

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The invention changes the physical and chemical parameters of the synthesis process by using aqueous sulphurous acid instead of gaseous sulphur dioxide and hydrogen. This parameter change from gas phase to aqueous phase allows for safer handling, better control of reaction conditions, and elimination of flammability and corrosion hazards associated with the gaseous reactants.

Inventive Principle:
Principle #35Parameter changes

2Quantity of substance

If existing supercapacitor electrode materials are used, then basic capacitance is achieved, but energy density is low and resistance is high

Engineering Contradiction:
Improveenergy densityVSAvoidresistance
Core Design Contradiction:
Quantity of substanceVSReliability

Solution Approach 1:

The patent creates a composite electrode material by combining lithium sulphite with a nitrogen-containing carbon structure. This composite approach allows the lithium sulphite to form SO3 complexes at nitrogen sites, creating a material that simultaneously achieves high energy density through complex formation and low resistance through the conductive carbon matrix.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The invention introduces local quality variations by incorporating lithium sulphite specifically at nitrogen-containing sites within the carbon structure. This localized complex formation at specific nitrogen sites creates regions of high capacitance while maintaining the overall conductivity of the carbon matrix, thereby achieving both high energy density and low resistance.

Inventive Principle:
Principle #3Local quality

3Area of stationary object

If pyrolysis temperature is increased to obtain high surface area, then surface area increases, but nitrogen content decreases

Engineering Contradiction:
Improvesurface areaVSAvoidnitrogen content
Core Design Contradiction:
Area of stationary objectVSQuantity of substance

Solution Approach 1:

The patent applies preliminary action by incorporating lithium sulphite into the carbon structure before final pyrolysis or during controlled heating stages. This preliminary incorporation ensures that nitrogen-containing functional groups are preserved and activated before excessive thermal degradation can occur, allowing subsequent formation of SO3 complexes without requiring extremely high pyrolysis temperatures that would degrade nitrogen content.

Inventive Principle:
Principle #10Preliminary action

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

The process yields a homogenized electrode material with lower resistance and higher energy density, capable of high power and long cycle life, as demonstrated by increased specific capacitance and stable performance over 10,000 cycles.

Implementation Method 1

reacting the H2SO3 (aq) with an aqueous suspension of Li2CO3 in the vessel to form an aqueous solution of Li2SO3

Methodology Applied
Scientific EffectChemical reaction: Chemical Bonding

Implementation Method 2

evaporating the solution to recover Li2SO3 (s)

Methodology Applied
Scientific EffectEvaporation: Evaporation

Implementation Method 3

forming N: sulphur trioxide SO3 complexes at the nitrogen sites

Methodology Applied
Scientific EffectComplex formation: Chemical Bonding

Data Source

PatentEP2609035B1Preparation of electrode compositions
Publication Date: 2016.10.05 QINETIQ LTD
  • EP2609035B1 patent drawingFigure 1~2
  • EP2609035B1 patent drawingFigure 3
  • EP2609035B1 patent drawingFigure 4~5

AI summary

The invention relates to processes for the preparation of electrode compositions, especially those intended for use in supercapacitors. A process is provided for preparing lithium sulphite comprising the steps of:- a) introducing H2SO3 (aq) into a reaction vessel; b) reacting the H2SO3 (aq) with an aqueous suspension of Li2CO3 in the vessel to form an aqueous solution of Li2CO3; and c) evaporating the solution to recover Li2CO3(s), wherein at least steps a) and b) are conducted under an inert atmosphere. Preferably, in step b) H2SO3 (aq) and Li2CO3 (aq) are reacted with each other in substantially equimolar amounts. There is also provided a process for forming an electrode material comprising a complexing step of causing lithium sulphite to form SO3 complexes at active N sites of a nitrogen-carbon structure, in the presence of a selected amount of a sink that absorbs the liberated lithium, so as to form the N:SO3 complexed electrode material. Preferably, the nitrogen-carbon structure is thermally restructured polyacrylonitrile (TR-PAN) or a copolymer thereof.